118422-65-4Relevant articles and documents
Reduction of ReCl5 in the presence of PMePh2 to give mer-ReCl3(PMePh2)3, ReCl(η2-H2)(PMePh2)4, ReH3(PMePh2)4, or ReCl(CO)3(PMePh2)2, depending on conditions
Cotton, F. Albert,Luck, Rudy L.
, p. 2181 - 2186 (2008/10/08)
Reduction of ReCl5 with excess magnesium in a THF/toluene (1:1) mixture in the presence of PMePh2 leads to the formation of mer-ReCl3(PMePh2)3 (1) in high yields. However, reduction with 4 equiv of Na affords ReCl(η2-H2)(PMePh2)4 (2), and when an excess of Na is employed, ReH3(PMePh2)4 (3) is obtained. The complex ReCl(CO)3(PMePh2)2 (4) is formed when solutions of 2 are placed under a CO atmosphere. The variable-temperature 1H and 31P NMR spectra of 2 and 3 are reported. The single-crystal X-ray structures of complexes 1 and 3 are reported. Crystal data: compound 1, monoclinic, space group P21/c, a = 11.429 (3) A?, b = 17.468 (6) A7ring;, c = 23.189 (6) A?, β = 97.88 (2)°, V = 4585 (7) A?3, Z = 4, R = 0.053 (Rw = 0.062) for 365 parameters and 2424 unique data having Fo > 3σ(Fo2); compound 3, triclinic, space group P1, a = 10.745 (4) A?, b = 22.136 (4) A?, c = 10.361 (2) A?, α = 98.51 (2)°, β = 109.12 (2)°, γ = 98.38 (2)°, V = 2252 (1) A?3, Z = 2, R = 0.054 (Rw = 0.093) for 447 parameters and 7440 unique data having Fo > 3σ(Fo2). The geometry of 3 is that of a distorted pentagonal bipyramid with PMePh2 ligands in the apical positions. The metal-bonded hydrogen atoms were located in the difference maps and refined to give an average Re-H distance of 1.76 [2] A? and a closest H-H distance of 1.96 (13) A?.
